JP2017034236A - Manufacturing method of wiring board, and wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a wiring board capable of easily forming a pattern even by using a coating composition indicating a high surface tension, and the wiring board.SOLUTION: The manufacturing method includes: a transfer step for bringing a resin composition containing a first compound presenting low surface free energy and a second compound presenting higher surface free energy than the first compound into contact with an original plate on which a pattern of a desired surface free energy difference is formed, hardening the resin composition and obtaining a substrate on which the pattern of the surface free energy difference of the original plate is transferred; and a conductor pattern formation step for coating a pattern transferred surface of the substrate with a conductive coating composition and forming a conductor pattern. The substrate includes patterns of a high surface free energy region and a low surface free energy region, and surface free energy in the high surface free energy region is higher than 62 mJ/m.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for manufacturing a wiring board and a wiring board for forming a conductor pattern on a base material on which a surface free energy difference of an original plate is transferred.

  Currently, most fine patterns of electronic circuits in semiconductors, displays, electronic products, and the like are produced using photolithography technology, but there is a limit to the production of inexpensive products using photolithography technology. In addition, in the manufacture of electronic products that aim to increase the area, it is difficult to reduce the manufacturing cost by a manufacturing method using a photolithography technique.

  In view of such a current situation, so-called “printed electronics” in which an electronic circuit, a sensor, an element, and the like are manufactured by utilizing a printing (printing) technique has been studied. This method can be expected to reduce the amount of chemical substances used, and is attracting attention as a manufacturing process friendly to the global environment. Some of these methods have already been applied to electrode printing of membrane keyboards, automotive window glass heat rays, RFID (Radio Frequency Identification) tag antennas, and the like.

  In printed electronics, it is important to control the wettability of the substrate (printed side). Control of wettability is achieved by controlling surface free energy, and various methods have been proposed. Among them, a substrate having a pattern of surface free energy difference has been proposed.

  For example, Patent Document 1 describes a technique in which a surface is modified with radiation or generated ozone through a mask, a pattern is formed by a surface free energy difference, ink is applied to the surface, and coating is performed separately. However, in the technique described in Patent Document 1, although the surface free energy difference is formed on the base material, since the surface free energy difference is small, when ink is applied to the surface, complete coating cannot be performed, It is only possible to make a difference in the film thickness of the coating film.

  In Patent Document 2, a low surface free energy part is partially created by exposure due to a difference in light transmittance of a Fresnel lens, and then an unexposed part is exposed in water to thereby obtain a high surface free energy part. Techniques for forming are described. In addition, a technique is described in which a pattern is formed by applying ink to a pattern created there and then peeling off unnecessary ink. However, in the technique described in Patent Document 2, although a surface free energy difference is formed on the base material as in Patent Document 1, it is not possible to separate the ink by simply applying ink on the surface. It is necessary to remove the ink from a portion (a portion having a low surface free energy) where it is not desired to adhere the ink.

  Patent Document 3 discloses a technique in which a surface is partially modified with radiation through a mask to form a pattern due to a surface free energy difference, and then a pattern is formed by transfer with heating and pressurization. Have been described. However, in the technique described in Patent Document 3, a pattern is formed by transferring a functional ink layer to a surface free energy pattern. However, heating and pressurization are required at the time of transfer, and a surplus is removed. is necessary.

  Patent Document 4 describes a technique for selectively applying a coating composition to a coating film onto which a surface free energy difference pattern of an original is transferred. However, with the technique described in Patent Document 4, it is difficult to selectively apply a coating composition exhibiting a high surface tension, for example, a water-based conductive coating composition to form a pattern.

JP 2005-52686 A JP 2003-240916 A JP 2011-14829 A JP, 2014-240137, A

  The present invention has been proposed in view of such a conventional situation, and a method of manufacturing a wiring board and a wiring that can easily form a pattern even when a coating composition exhibiting a high surface tension is used. Providing a substrate.

In order to solve the above-described problems, a method for manufacturing a wiring board according to the present invention includes a first compound that exhibits low surface free energy and a second compound that exhibits higher surface free energy than the first compound. A step of transferring a resin composition containing a compound to a master on which a pattern of a desired surface free energy difference is formed and curing to obtain a substrate on which the pattern of the surface free energy difference of the original is transferred; A conductive pattern forming step of applying a conductive coating composition to a pattern transfer surface of the base material to form a conductive pattern, and the base material has a pattern of a high surface free energy region and a low surface free energy region. And the surface free energy of the high surface free energy region is higher than 62 mJ / m ² .

The wiring board according to the present invention includes a base material having a pattern of a high surface free energy region and a low surface free energy region, and a conductor pattern formed on the high surface free energy region, the high surface free energy The surface free energy in the energy region is higher than 62 mJ / m ² .

Moreover, the manufacturing method of the pattern formation body which concerns on this invention is resin containing the 1st compound which expresses low surface free energy, and the 2nd compound which expresses surface free energy higher than the said 1st compound. The composition is brought into contact with an original plate on which a desired surface free energy difference pattern is formed and cured to obtain a substrate on which the surface free energy difference pattern of the original plate is transferred, and pattern transfer of the substrate A pattern forming step of applying a conductive coating composition to a surface to form a pattern, wherein the substrate has a pattern of a high surface free energy region and a low surface free energy region, and the high surface free energy The surface free energy of the region is higher than 62 mJ / m ² .

The pattern forming body according to the present invention comprises a substrate having a pattern of a high surface free energy region and a low surface free energy region, and a pattern formed on the high surface free energy region, and the high surface free energy The surface free energy in the energy region is higher than 62 mJ / m ² .

Further, the base material according to the present invention is cured by a resin composition containing a first compound that expresses low surface free energy and a second compound that expresses higher surface free energy than the first compound. The substrate thus formed has a pattern of a high surface free energy region and a low surface free energy region, and the surface free energy of the high surface free energy region is higher than 62 mJ / m ² .

  Moreover, the resin composition according to the present invention contains a first compound that expresses low surface free energy and a second compound that expresses higher surface free energy than the first compound, and the second compound. The compound of 1 contains monofunctional (meth) acrylate, and content of the said monofunctional (meth) acrylate is 40-70 mass parts with respect to 100 mass parts of said 2nd compounds, It is characterized by the above-mentioned.

  According to this invention, since the surface free energy of the high surface free energy area | region of a base material is high, the coating composition which shows high surface tension can be used, and a pattern can be formed simply.

FIG. 1 is a cross-sectional view illustrating an outline of a coating process for coating a resin composition on a support film. FIG. 2 is a cross-sectional view showing an outline of a curing step in which the resin composition is cured by contacting the original plate. FIG. 3 is a cross-sectional view showing an example of a substrate to which a pattern is transferred. FIG. 4 is a cross-sectional view showing an example of a wiring board having a conductor pattern formed on the surface of a base material. FIG. 5 is a perspective view showing an outline of the original A. FIG. FIG. 6 is a cross-sectional view schematically showing a transfer process for transferring the pattern of the original A. FIG. 7 is an observation image of the conductor pattern formed on the base material A3 in Example 1 with an optical microscope. FIG. 8 is an observation image of the conductor pattern formed on the base material A4 in Example 2 with an optical microscope. FIG. 9 is an observation image of the conductor pattern formed on the base material A1 in Comparative Example 1 with an optical microscope. FIG. 10 is an observation image of the conductor pattern formed on the base material A2 in Comparative Example 2 with an optical microscope.

Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. 1. Manufacturing method of wiring board 2. Wiring board Other Embodiment 4 Example

<1. Manufacturing method of wiring board>
The manufacturing method of the wiring board which concerns on one embodiment of this invention contains the 1st compound which expresses low surface free energy, and the 2nd compound which expresses surface free energy higher than a 1st compound. A resin composition is brought into contact with an original plate on which a desired surface free energy difference pattern is formed and cured to obtain a substrate on which the surface free energy difference pattern of the original plate is transferred, and pattern transfer of the substrate A conductive pattern forming step of applying a conductive coating composition to the surface to form a conductive pattern. Here, the substrate has a pattern of a high surface free energy region and a low surface free energy region, and the surface free energy of the high surface free energy region is higher than 62 mJ / m ² , thereby exhibiting a high surface tension. A composition can be used, for example, an aqueous conductive coating composition can be selectively applied to form a conductive pattern.

[Transfer process]
In the transfer step, first, a resin composition containing a first compound that expresses low surface free energy and a second compound that expresses higher surface free energy than the first compound is prepared. Examples of the resin composition include an acrylic resin and an epoxy resin. Among these, a photo-curable acrylic resin composition having a fast curing reaction is preferably used. Hereinafter, a photocurable acrylic resin composition containing a first compound, a second compound, and a photopolymerization initiator will be described as an example.

  As the first compound, it is possible to use a surface conditioner such as a so-called “antiblocking agent”, “slipping agent”, “leveling agent”, “antifouling agent” or the like that expresses low surface free energy, A fluororesin compound such as a perfluoropolyether derivative or a silicone resin compound is preferably used. Examples of fluororesin compounds include perfluoropolyether group-containing (meth) acrylates and perfluoroalkyl group-containing (meth) acrylates, and silicone resin compounds include polydimethylsiloxane-containing (meth) acrylates and polyalkyls. Examples thereof include siloxane-containing (meth) acrylate. These may be used alone or in combination of two or more. Among these, perfluoropolyether group-containing (meth) acrylates can be preferably used from the viewpoint of solubility and the like. Examples of commercially available perfluoropolyether group-containing (meth) acrylates include trade name “KY-1203” (Shin-Etsu Chemical Co., Ltd.). In addition, in this specification, (meth) acrylate is meant to include acrylic acid ester (acrylate) and methacrylic acid ester (methacrylate).

  If the content of the first compound in the resin composition is too small, a pattern of surface free energy difference cannot be obtained. If the content is too large, the surface free energy difference tends to decrease. It is 0.01 mass part or more and 30 mass parts or less with respect to 100 mass parts, More preferably, it is 0.1 mass part or more and 10 mass parts or less.

  The 2nd compound should just be a compound which expresses higher surface free energy than the 1st compound, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or more (meth) acrylate, etc. Is mentioned.

  Examples of monofunctional (meth) acrylates include polyalkylene glycol ester monomers and alkyl (meth) acrylates having a linear or branched alkyl group. Specific examples of the polyalkylene glycol ester monomer include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono ( (Meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate and the like can be mentioned, and one or more of these can be used. Among these, polyethylene glycol mono (meth) acrylate can be preferably used in terms of reactivity, crosslinkability, surface hardness, and the like. Examples of commercially available products of polyethylene glycol mono (meth) acrylate include trade name “AE-400” (NOF Corporation).

  Specific examples of the bifunctional (meth) acrylate include, for example, tricyclodecane dimethanol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, bisphenol AEO-modified di (meth) acrylate, and 1,9-nonane. Diol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, diethylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polyethylene glycol (200) di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol (400) di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, alkoxylated cyclohexanedimethanol di (meth) acrylate, ethoxylated (4) bisphenol A di ( (Meth) acrylate, ethoxylated (10) bisphenol A di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, dioxane glycol di (meth) acrylate, isocyanuric acid EO Modified di (meth) acrylate etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  Specific examples of tri- or higher functional (meth) acrylates include pentaerythritol tri (meth) acrylate, propylene glycol-modified glycerin triacrylate, EO-modified pentaerythritol tri (meth) acrylate, isocyanuric acid EO-modified tri (meth) ) Acrylate, ε-caprolactone modified tris-(-2-acryloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, ε-caprolactone modified tris (acryloxyethyl) (meth) acrylate, ethoxylated (20) tri Methylolpropane tri (meth) acrylate, propoxylated (3) trimethylolpropane tri (meth) acrylate, propoxylated (6) trimethylolpropane tri (meth) acrylate, ethoxylated (9) trimethylo Propanetri (meth) acrylate, propoxylated (3) glyceryl tri (meth) acrylate, ethoxylated (4) pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Examples include erythritol penta (meth) acrylate, EO-modified dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, and one or more of these can be used. Among these, pentaerythritol tri (meth) acrylate and propylene glycol-modified glycerin triacrylate can be preferably used in terms of reactivity, crosslinkability, surface hardness, and the like. Examples of commercially available products of pentaerythritol tri (meth) acrylate include “TMM-3” (Shin Nakamura Chemical Co., Ltd.), and examples of commercially available products of propylene glycol-modified glycerin triacrylate include “ OTA-480 "(Daicel Ornex Co., Ltd.).

  The second compound contains a monofunctional (meth) acrylate, and the content of the monofunctional (meth) acrylate is preferably 40 to 70 parts by mass with respect to 100 parts by mass of the second compound. When the content of the monofunctional (meth) acrylate is too small, it is difficult to obtain high surface free energy. When the content is too large, the reactivity, crosslinkability and the like tend to decrease.

  As a photoinitiator, it can select from a well-known radical photopolymerization initiator suitably, and can use it. Examples of the photopolymerization initiator include α-hydroxyalkylphenone, benzyldimethyl ketal, α-aminoalkylphenone, and the like, and one or more of these can be used.

  Specific examples of photopolymerization initiators available on the market include 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, BASF Japan Ltd.), 2-hydroxy-2 as α-hydroxyalkylphenone. -Methyl-1-phenyl-propan-1-one (DAROCUR 1173, BASF Japan Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -Propan-1-one (IRGACURE 2959, BASF Japan Ltd.), 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2-methyl- Propan-1-one (IRGACURE 127, BAS Such as Japan Co., Ltd.) and the like. Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651, BASF Japan Ltd.). Further, as α-aminoalkylphenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907, BASF Japan Ltd.), 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369, BASF Japan Ltd.) and the like. Among these, it is preferable to use 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, BASF Japan Ltd.) from the viewpoint of realizing smooth photocuring.

  If the content of the photopolymerization initiator in the resin composition is too small, there is a tendency that the adhesiveness is lowered or the hardness is insufficient due to a decrease in hardness performance. Since there exists a tendency, Preferably they are 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of 2nd compounds, More preferably, they are 1 mass part or more and 5 mass parts or less.

  Further, the resin composition contains additives such as a solvent, a leveling agent, a hue adjusting agent, a colorant, an ultraviolet absorber, an antistatic agent, and various thermoplastic resin materials as long as the effects of the present invention are not impaired. Can do.

  FIG. 1 is a cross-sectional view illustrating an outline of a coating process for coating a resin composition on a support film. For coating, a bar coater, spray coater, spin coater or the like can be used.

  The support film 11 is not particularly limited, and PET (Polyethylene terephthalate), glass, polyimide, or the like can be used. Moreover, although either a transparent material or an opaque material can be used, ultraviolet rays can be irradiated from the support film 11 side by using a transparent material that transmits ultraviolet rays.

  As described above, the resin composition 12 contains the first compound, the second compound, and the photopolymerization initiator, and the first compound is present on the surface. In addition, in FIG. 1, although a fluororesin type compound is illustrated as a 1st compound, it is not limited to this.

  Next, in the transfer process, the resin composition 12 is brought into contact with the original 20 and cured to obtain a substrate on which the pattern of the surface free energy difference of the original 20 is transferred.

  FIG. 2 is a cross-sectional view showing an outline of a curing step in which the resin composition is cured by contacting the original plate. In this curing step, the resin composition 12 is brought into contact with the original plate 20 on which the pattern due to the surface free energy difference is formed and cured to form a cured resin layer on which the pattern of the original plate 20 is transferred on the support film 11.

  The original 20 has a high surface free energy region 21 and a low surface free energy region 22 on the surface. The high surface free energy region 21 is a region such as a metal oxide including a metal such as silicon, aluminum, or copper, glass, silicon oxide, or aluminum oxide, and the low surface free energy region 22 is, for example, a fluorine coating, This is a region of a low surface free energy coating film such as a silicone coating, or an inert gas such as nitrogen or carbon dioxide. The material of the original 20 is preferably glass that can be easily coated with fluorine. Further, the surface of the original 20 is preferably smooth.

  As shown in FIG. 2, when the original 20 is brought into contact with the resin composition 12, the interface state between the original 20 and the resin composition 12 tends to decrease Δγ in the following formula (1). The first compound on the 12 surface moves to the low surface free energy region 21 of the original 20, and the second compound moves to the high surface free energy region 22. In addition, although a fluororesin type compound is illustrated as a 1st compound in FIG. 2, it is not limited to this.

Δγ = γ _m −γ _i (1)
In the above formula (1), γ _m is the surface free energy on the surface of the original 20, and γ _i is the surface free energy on the surface of the resin composition 12.

  By curing the resin composition 12 in a state where the original plate 20 is in contact with the resin composition 12, it is possible to obtain a base material 13 made of a cured resin layer in which the pattern of the original plate 20 is transferred onto the support film 11. The curing method of the resin composition 12 can be appropriately selected according to the type of the resin, and irradiation with energy rays such as heat and ultraviolet rays can be used.

  FIG. 3 is a cross-sectional view showing an example of a substrate to which a pattern is transferred. In addition, in FIG. 3, although a fluororesin type compound is illustrated as a 1st compound, it is not limited to this.

  The base material 13 has a pattern of a high surface free energy region a and a low surface free energy region b on the surface of the cured resin layer. The substrate 13 is obtained by curing a resin composition containing a first compound that expresses low surface free energy and a second compound that expresses higher surface free energy than the first compound. Have a high surface free energy region a and a low surface free energy region b. Moreover, it is preferable that the high surface free energy area | region a and the low surface free energy area | region b are optically smooth surfaces, and the level | step difference of both is less than several tens of nm.

The high surface free energy region a is higher than 62 mJ / m ² , and the difference in surface free energy between the high surface free energy region a and the low surface free energy region b is preferably 30 mJ / m ² or more. More specifically, the surface free energy of the high surface free energy area a is preferably 63~80mJ / ^{m 2,} and more preferably 66~75mJ / ^{m 2.} The surface free energy of a low surface free energy area b is preferably 10~25mJ / ^{m 2,} and more preferably 10~20mJ / ^{m 2.} Accordingly, the conductive coating composition can be selectively applied to the high surface free energy region a by using a simple construction method, for example, a printing method such as dipping, without using a complicated apparatus. In particular, in this embodiment, since the surface free energy in the high surface free energy region of the substrate is high, an aqueous coating composition exhibiting a high surface tension can be used, and the variation of the coating composition can be increased. it can.

[Conductor pattern forming process]
In the conductor pattern forming step, the conductive coating composition is applied to the pattern transfer surface of the substrate to form a conductor pattern. The conductor pattern is selectively formed on the high surface free energy portion or the low surface free energy portion.

  Examples of the coating method of the conductive coating composition include dip coating, spin coating, flow coating, spray coating, and squeegee method. Among these, it is preferable to use dip coating with a simple apparatus.

  The conductive coating composition is selectively applied to a high surface free energy region or a low surface free energy region on the substrate surface, and becomes a conductor pattern by drying, heating, firing, or the like. Examples of the conductive coating composition include what are called conductive inks and metal inks in which metal particles having a particle diameter of 1 to 100 nm are dispersed in a solvent at a high concentration. Examples of the metal particles include conductive metals such as silver, gold, copper, nickel, and palladium. Among these, it is preferable to use silver exhibiting high conductivity. Moreover, it is preferable that an electroconductive coating composition contains an organic compound (ligand) and dissolves metal particles in a solution by the dispersing power of the ligand. Moreover, as a solvent, it is preferable from a soluble viewpoint of a ligand to use polar solvents, such as water, methanol, and ethanol, and an electroconductive coating composition shows hydrophilicity. Commercially available conductive coating compositions include, for example, trade names “TEC-PR-010” (InkTec Co., Ltd.), “TEC-IJ-010” (InkTec Co., Ltd.), “Dry Cure Ag” (Colloidal Ink Co., Ltd.).

When a coating composition exhibiting a high surface tension is used, the surface free energy in the high surface free energy region is preferably higher than −10 mJ / m ² of the surface free energy of the coating composition, and is −6 mJ / m ² or higher. It is more preferable. That is, the surface free energy in the high surface free energy region is preferably lower than the surface free energy of the coating composition by less than 10 mJ / m ² , more preferably 6 mJ / m ² or less. In order to obtain good adhesion between the substrate and the coating composition (ink), it is necessary for the ink to sufficiently wet the substrate surface. Depending on the surface tension, the substrate tends to wet well when the surface tension of the substrate is greater than the surface tension of the ink. The surface tension is the surface free energy per unit area. If the surface tension of the surface of a liquid is γ (mN / m), the surface free energy of the liquid is γ (mJ / m ² ) It is the same as that.

  As described above, in the conductor pattern forming process, by using a base material having a high surface free energy in the high surface free energy region, an aqueous conductive coating composition exhibiting a high surface tension is selectively applied by coating. Thus, it is possible to easily draw a wiring pattern having a fine pitch and excellent dimensional stability.

  Further, in the conductor pattern forming process, there are no complicated processes such as an exposure process using a photomask and a photoresist process, and a process for stripping off the excess of the conductive coating composition is not required. For this reason, a conductor pattern can be obtained with a required amount of conductive coating composition.

<2. Wiring board>
A wiring board according to an embodiment of the present invention includes a substrate having a pattern of a high surface free energy region and a low surface free energy region, and a conductor pattern formed on the high surface free energy region, and has a high surface. The surface free energy in the free energy region is higher than 62 mJ / m ² . Thereby, a conductor pattern can be formed with the water-system conductive coating composition which shows high surface tension.

  FIG. 4 is a cross-sectional view showing an example of a wiring board having a conductor pattern formed on the surface of a base material. As shown in FIG. 4, the wiring board has a substrate 13 having a low surface free energy region and a high surface free energy region on the surface, and a conductive pattern 14 formed in the high surface free energy region on the support film 11. With. In addition, in FIG. 4, although a fluororesin type compound is illustrated as a 1st compound, it is not limited to this. Moreover, since the support film 11 and the base material 13 are the same as the support film 11 and the base material 13 shown in FIGS. 1-3, description is abbreviate | omitted here.

  The conductive pattern is formed by adhering the conductive coating composition described above to a high surface free energy region on the surface of the substrate 13 by drying, heating, firing, or the like.

The conductor pattern is formed on the high surface free energy region, and the surface free energy in the low surface free energy region where the conductor pattern is not formed is preferably 10 to 25 mJ / m ² , and 10 to ²⁰ mJ / m ^2. more preferably m ^2. As a result, the conductive coating composition does not stay between the wirings, and it is possible to prevent a short circuit between the wirings. Therefore, the wiring board according to the present embodiment is very useful in the field of electronics such as electronic circuit patterns.

<3. Other embodiments>
In the above-described embodiment, the formation of the conductor pattern has been described. However, the present invention is not limited to the formation of the conductor pattern, and can be applied to the formation of a non-conductive pattern. That is, the manufacturing method of the pattern formation body which concerns on one embodiment of this invention is the 1st compound which expresses low surface free energy, and the 2nd compound which expresses surface free energy higher than a 1st compound, A transfer step for obtaining a base material on which the pattern of the surface free energy difference of the original plate is transferred by curing the resin composition containing the resin on the original plate on which the pattern of the desired surface free energy difference is formed; A pattern forming step of applying a coating composition on the pattern transfer surface to form a pattern. Here, the substrate has a pattern of a high surface free energy region and a low surface free energy region, and the surface free energy of the high surface free energy region is higher than 62 mJ / m ² , thereby exhibiting a high surface tension. The composition can be selectively applied to form a pattern.

Further, a pattern forming body according to an embodiment of the present invention comprises a substrate having a pattern of a high surface free energy region and a low surface free energy region, and a pattern formed on the high surface free energy region, The surface free energy in the high surface free energy region is higher than 62 mJ / m ² . Thereby, even when the coating composition which shows high surface tension is used, the adhesiveness of the pattern on a high surface free energy area | region can be improved.

Moreover, the base material which concerns on one embodiment of this invention contains the 1st compound which expresses low surface free energy, and the 2nd compound which expresses surface free energy higher than the said 1st compound. The base material formed by curing the resin composition has a pattern of a high surface free energy region and a low surface free energy region, and the surface free energy of the high surface free energy region is higher than 62 mJ / m ² . As a result, even when a coating composition showing a high surface tension is used, a pattern can be formed on the high surface free energy region.

The resin composition according to one embodiment of the present invention contains a first compound that expresses low surface free energy and a second compound that expresses higher surface free energy than the first compound. The second compound contains a monofunctional (meth) acrylate, and the content of the monofunctional (meth) acrylate is 40 to 70 parts by mass with respect to 100 parts by mass of the second compound. Thereby, the surface free energy of the high surface free energy area | region of the base material after hardening can be made higher than 62 mJ / m < ² >.

<4. Example>
Examples of the present invention will be described in detail below. In this example, a master A having a pattern formed by a difference in surface free energy, a master B having a low surface free energy over the entire surface, and a master C having a high surface free energy over the entire surface are prepared. The resin composition was transferred. The present invention is not limited to these examples.

The following apparatus was used for the exposure machine, contact angle meter, microscope, and AFM (Atomic Force Microscope).
Exposure machine A: Mask aligner MA-20 (Mikasa Co., Ltd.)
Exposure machine B: Alignment exposure system (manufactured by Toshiba Lighting & Technology Corp.)
Contact angle meter: DM-701 (manufactured by Kyowa Interface Science Co., Ltd.)
Microscope: VHX-1000 (manufactured by Keyence Corporation)
AFM: SPA400 (manufactured by Hitachi High-Tech Science Co., Ltd.)

[Create original A]
A negative photoresist (trade name: OFPR-800LB, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to a 10 cm × 10 cm glass substrate by a spin coating method, and dried on a hot plate at 110 ° C. for 90 seconds. A substrate coated with a photoresist and a photomask patterned with 5 μm lines and spaces were placed and exposed with an exposure machine A. After exposure, the substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, then immersed in pure water for 1 minute, dried at room temperature, and developed.

  The developed substrate was cleaned in the order of pure water and a cleaning solution (trade name: Novec 7300, manufactured by 3M), and then a fluorine coating agent (trade name: DS-5210F, manufactured by HARVES) was applied by droplet dropping. . After being left overnight, it was washed with a cleaning solution (trade name: Novec 7300, manufactured by 3M), and then a fluorine coating agent (trade name: DS-5210F, manufactured by HARVS) was applied by droplet dropping. Furthermore, after leaving overnight, it wash | cleaned with the washing | cleaning liquid (Brand name: Novec7300, 3M company make), and dried at room temperature.

  This substrate was immersed in a stripping solution for 5 minutes, the remaining resist film was removed, and the substrate was washed with acetone and a cleaning solution (trade name: Novec 7300, manufactured by 3M) in this order. As a result, as shown in FIG. 5, an original A having a high surface free energy region 31 and a low surface free energy region 32 patterned (partially fluorine coated) on the glass substrate 30 was obtained.

[Create Master B]
A slide glass of 7 cm × 5 cm was washed with a washing liquid (trade name: Novec 7300, manufactured by 3M), and then a fluorine coating agent (trade name: DS-5210F, manufactured by HARVES) was applied dropwise. After being left overnight, it was washed with a cleaning solution (trade name: Novec 7300, manufactured by 3M), and then a fluorine coating agent (trade name: DS-5210F, manufactured by HARVES) was applied by droplet dropping. Further, after being left overnight, it was washed with a cleaning solution (trade name: Novec 7300, manufactured by 3M) to obtain an original plate B (the entire surface was coated with fluorine).

[Create original version C]
An unused 7 cm × 5 cm glass slide was used as an original C.

[Ink composition]
Table 1 shows the compositions of inks 1-6.

TMM-3 (Shin Nakamura Chemical Co., Ltd.): Pentaerythritol triacrylate OTA-480 (Daicel Ornex Co.): Propylene glycol-modified glycerin triacrylate AE-400 (Nippon Oil Co., Ltd.): Polyethylene glycol monoacrylate # 400
Irgacure 184 (BASF Corp.): 1-hydroxycyclohexyl phenyl ketone KY-1203 (Shin-Etsu Chemical Co., Ltd.): Perfluoropolyether-containing acrylate

[Production of substrate]
FIG. 6 is a cross-sectional view schematically showing a transfer process for transferring the pattern of the original A. As shown in FIG. 6, inks 1 to 6 are applied onto a PET film with a bar coater (equivalent to a wet film thickness of 8 μm) and brought into close contact with the original A, and an exposure machine B (alignment exposure apparatus, Toshiba Lighting & Technology Corp.). ) Was exposed and cured from the PET surface to obtain a substrate having a cured resin layer. The irradiation dose at this time was 6 J / cm ² . The original A was peeled from the surface of the cured resin layer to obtain base materials A1 to A6 having a cured resin layer on which the surface free energy of the original A was transferred onto a PET film. Similarly, for the original plate B and the original plate C, the inks 1 to 6 were cured to obtain base materials B1 to B6 and base materials C1 to C6 to which surface free energy was transferred.

[Calculation of surface free energy]
Table 2 shows the surface free energy of the base material B and the base material C. The surface free energy was calculated by the Kelble-Wu method by measuring the contact angles of the substrates B1 to B6 and the substrates C1 to C6 using a contact angle meter. Thereby, base material A1-A6 low surface free energy area | region is regarded as surface free energy of base material B1-B6, respectively, and high surface free energy area | region of base material A1-A6 is the surface free energy of base material C1-C6, respectively. Regarded as energy.

[Evaluation of coating characteristics]
A metal ink (Dry Cure Ag, Colloidal Ink Co., Ltd., surface tension: 72 mN / m) was filled in the sample bottle. Base materials A1 to C6 were dipped in this sample bottle, pulled up vertically at a speed of 1 cm / min, and left at room temperature for 10 minutes. The surface after coating was observed with an optical microscope at 2000 times. When the pattern is applied on the observation surface, it is evaluated as “○”, and when it is not applied as a pattern in some areas on the observation surface, it is evaluated as “△”. The case where it was not evaluated was evaluated as “×”.

<Example 1>
Ink 3 is applied onto a PET film with a bar coater (equivalent to a wet film thickness of 8 μm), and this is brought into close contact with the original A and exposed and cured from the PET surface using an exposure machine B (alignment exposure device, Toshiba Lighting & Technology Corp.). To form a cured resin layer. The irradiation dose at this time was 6 J / cm ² . The original A was peeled from the surface of the cured resin layer to obtain a substrate A3 having a cured resin layer on which the surface free energy of the original A was transferred onto a PET film. Similarly, the ink 3 was exposed and cured using the original plate B and the original plate C to obtain a base material B3 and a base material C3.

As shown in Table 3, the surface free energy of the substrate B3 was 17 mJ / m ² , and the surface free energy of the substrate C3 was 66 mJ / m ² . Therefore, the surface free energy in the low surface free energy region of the substrate A3 was regarded as 17 mJ / m ² , and the surface free energy in the high surface free energy region was regarded as 66 mJ / m ² . Further, the difference between the surface free energy in the high surface free energy region and the surface tension of the metal ink was regarded as 6 mJ / m ² . FIG. 7 is an observation image of the conductor pattern formed on the base material A3 in Example 1 with an optical microscope. The conductive coating composition was selectively applied only to the high surface free energy portion, and the evaluation of the coating property was ◯.

<Example 2>
Substrate A4, substrate B4, and substrate C4 were obtained in the same manner as in Example 1 except that ink 4 was used. As shown in Table 3, the surface free energy of the base material B4 was 17 mJ / m ² , and the surface free energy of the base material C4 was 69 mJ / m ² . Therefore, the surface free energy in the low surface free energy region of the substrate A4 was regarded as 17 mJ / m ² , and the surface free energy in the high surface free energy region was regarded as 69 mJ / m ² . Further, the difference between the surface free energy in the high surface free energy region and the surface tension of the metal ink was regarded as 3 mJ / m ² . FIG. 8 is an observation image of the conductor pattern formed on the base material A4 in Example 2 with an optical microscope. The conductive coating composition was selectively applied only to the high surface free energy portion, and the evaluation of the coating property was ◯.

<Example 3>
Substrate A5, substrate B5, and substrate C5 were obtained in the same manner as in Example 1 except that ink 5 was used. As shown in Table 3, the surface free energy of the substrate B5 was 17 mJ / m ² , and the surface free energy of the substrate C5 was 68 mJ / m ² . Therefore, the surface free energy in the low surface free energy region of the substrate A5 was regarded as 17 mJ / m ² and the surface free energy in the high surface free energy region was regarded as 68 mJ / m ² . Further, the difference between the surface free energy in the high surface free energy region and the surface tension of the metal ink was regarded as 4 mJ / m ² . As a result of observation with an optical microscope, the conductive coating composition was selectively applied only to the high surface free energy portion, and the evaluation of the color separation property was good.

<Example 4>
Substrate A6, substrate B6, and substrate C6 were obtained in the same manner as in Example 1 except that ink 6 was used. As shown in Table 3, the surface free energy of the substrate B6 was 17 mJ / m ² , and the surface free energy of the substrate C5 was 63 mJ / m ² . Therefore, the surface free energy in the low surface free energy region of the substrate A6 was regarded as 17 mJ / m ² and the surface free energy in the high surface free energy region was regarded as 63 mJ / m ² . Further, the difference between the surface free energy in the high surface free energy region and the surface tension of the metal ink was regarded as 9 mJ / m ² . As a result of observation with an optical microscope, it was not possible to apply as a pattern in a partial region on the observation surface, and the evaluation of the coating property was Δ.

<Comparative Example 1>
Substrate A1, substrate B1, and substrate C1 were obtained in the same manner as in Example 1 except that ink 1 was used. As shown in Table 3, the surface free energy of the substrate B1 was 16 mJ / m ² , and the surface free energy of the substrate C1 was 51 mJ / m ² . Therefore, the surface free energy in the low surface free energy region of the substrate A1 was regarded as 16 mJ / m ² , and the surface free energy in the high surface free energy region was regarded as 51 mJ / m ² . Further, the difference between the surface free energy in the high surface free energy region and the surface tension of the metal ink was regarded as 21 mJ / m ² . FIG. 9 is an observation image of the conductor pattern formed on the base material A1 in Comparative Example 1 with an optical microscope. It was not able to be applied according to the pattern on the observation surface, and the evaluation of the color separation property was x.

<Comparative example 2>
Substrate A2, substrate B2, and substrate C2 were obtained in the same manner as in Example 1 except that ink 2 was used. As shown in Table 3, the surface free energy of the substrate B2 was 15 mJ / m ² , and the surface free energy of the substrate C2 was 62 mJ / m ² . Therefore, the surface free energy in the low surface free energy region of the substrate A2 was regarded as 15 mJ / m ² , and the surface free energy in the high surface free energy region was regarded as 62 mJ / m ² . Further, the difference between the surface free energy in the high surface free energy region and the surface tension of the metal ink was regarded as 10 mJ / m ² . FIG. 10 is an observation image of the conductor pattern formed on the base material A2 in Comparative Example 2 with an optical microscope. It was not able to be applied according to the pattern on the observation surface, and the evaluation of the color separation property was x.

As in Comparative Examples 1 and 2, when the surface free energy in the high surface free energy region of the base material was 62 mJ / m ² or less, it was difficult to separately coat metal ink exhibiting high surface tension. On the other hand, as in Examples 1 to 4, when the surface free energy in the high surface free energy region of the substrate was higher than 62 mJ / m ² , the metal ink exhibiting high surface tension could be applied separately.

Further, from Examples 1 to 4, the surface free energy in the high surface free energy region is higher than −10 mJ / m ² of the surface free energy of the coating composition, and is −6 mJ / m ² or more. The surface free energy in the high surface free energy region is less than the surface free energy of the coating composition by less than 10 mJ / m ² , and further 6 mJ / m ² or less, which indicates that excellent coating characteristics can be obtained. It was. This is presumably because the metal ink was well wetted on the substrate surface.

  Moreover, from Examples 1-4, a base material is produced using the ink 3-6 whose content of monofunctional (meth) acrylate is 40-70 mass parts with respect to 100 mass parts of all (meth) acrylates. Thus, even when a metal ink exhibiting a high surface tension was used, it was found that it could be selectively applied by a simple method by dipping.

DESCRIPTION OF SYMBOLS 11 Support film, 12 Resin composition, 13 Base material, 14 Conductor pattern, 20 Original plate, 21 Low surface free energy region, 22 High surface free energy region, 30 Glass substrate, 31 Low surface free energy region, 32 High surface free energy Area, 41 PET film, 42 resin composition

Claims (15)

A desired surface free energy difference pattern is formed from a resin composition containing a first compound that develops low surface free energy and a second compound that develops higher surface free energy than the first compound. A transfer step of obtaining a base material on which the pattern of the surface free energy difference of the original plate is transferred by being brought into contact with the prepared original plate and cured;
A conductive pattern forming step of applying a conductive coating composition to the pattern transfer surface of the substrate and forming a conductive pattern;
The substrate has a pattern of a high surface free energy region and a low surface free energy region;
A method for manufacturing a wiring board, wherein the surface free energy in the high surface free energy region is higher than 62 mJ / m ² . The method for manufacturing a wiring board according to claim 1, wherein a surface free energy of the high surface free energy region is higher than −10 mJ / m ² of a surface free energy of the conductive coating composition. The manufacturing method of the wiring board of Claim 1 or 2 whose surface free energy of the said low surface free energy area | region is 10-20 mJ / m < ² >.   The manufacturing method of the wiring board of any one of Claim 1 thru | or 3 in which the said electroconductive coating composition contains silver.   The method for manufacturing a wiring board according to claim 1, wherein the first compound is a perfluoropolyether derivative. The second compound comprises a monofunctional (meth) acrylate;
The manufacturing method of the wiring board of any one of Claims 1 thru | or 5 whose content of the said monofunctional (meth) acrylate is 40-70 mass parts with respect to 100 mass parts of said 2nd compounds. A substrate having a pattern of a high surface free energy region and a low surface free energy region;
A conductor pattern formed on the high surface free energy region,
The wiring board having a surface free energy in the high surface free energy region higher than 62 mJ / m ² . The conductor pattern is formed from a conductive coating composition,
The wiring board according to claim 7, wherein a surface free energy of the high surface free energy region is higher than −10 mJ / m ² of a surface free energy of the coating composition. The wiring board according to claim 7 or 8, wherein the surface free energy of the low surface free energy region is 10 to ²⁰ mJ / m ² .   The wiring board according to claim 8, wherein the conductive coating composition contains silver. A desired surface free energy difference pattern is formed from a resin composition containing a first compound that develops low surface free energy and a second compound that develops higher surface free energy than the first compound. A transfer step of obtaining a base material on which the pattern of the surface free energy difference of the original plate is transferred by being brought into contact with the prepared original plate and cured;
Applying a coating composition to the pattern transfer surface of the substrate, and forming a pattern; and
The substrate has a pattern of a high surface free energy region and a low surface free energy region;
The manufacturing method of the pattern formation body whose surface free energy of the said high surface free energy area | region is higher than 62 mJ / m < ² >. A substrate having a pattern of a high surface free energy region and a low surface free energy region;
A pattern formed on the high surface free energy region,
The pattern formation body whose surface free energy of the said high surface free energy area | region is higher than 62 mJ / m < ² >. In a substrate formed by curing a resin composition containing a first compound that expresses low surface free energy and a second compound that expresses higher surface free energy than the first compound,
Having a pattern of high surface free energy region and low surface free energy region,
The base material whose surface free energy of the said high surface free energy area | region is higher than 62 mJ / m < ² >. A first compound that exhibits low surface free energy;
A second compound that expresses a higher surface free energy than the first compound,
The second compound comprises a monofunctional (meth) acrylate;
The resin composition whose content of the said monofunctional (meth) acrylate is 40-70 mass parts with respect to 100 mass parts of said 2nd compounds. The resin composition according to claim 14, wherein the first compound is a perfluoropolyether derivative.